Water-insoluble azo dyestuffs and fiber dyed therewith



Patented Jan. 3, 1939 UNITED STATES PATENT OFFICE WATER-INSOLUBLE AZO DYESTUFFS AND FIBER DYED THEREWITH No Drawing. Application September 6, 1935, Se-

rial No. 39,501. In Germany September 12,

6 Claims.

The present invention relates to valuable water-insoluble azo dyestufls and to fiber dyed therewith; more particularly it relates to dyestuffs corresponding to the following general formula:

halogen wherein X and Y stand for alkyl or alkoxy, Y meaning alkoxy in case X stands for alkyl, and alkyl in case X stands for alkoxy, and wherein the benzene nucleus I may be further substituted by halogen, alkyl, alkoxy or aryloxy groups.

We have found that valuable water-insoluble azo dyestufis are obtainable by coupling in substance, on the fiber or on a substratum adapted for the production of lakes arylides of acetoacetic acid of the following formula:

NH.CQ.OHa.CO.CHa

halogen wherein X and Y stand for alkyl or alkoxy, Y meaning alkoxy incase X stands for alkyl, and alkyl in case X stands for alkoxy, with diazocompounds from, mono-amines of the benzene series which contain as substituents at least one halogen atom and, if desired, halogen, alkyl, alkyloxy or aryloxy groups.

When produced in substance, the new dyestufis may be used for the preparation of valuable pigments, but they may also be used with advantage for the preparation of water-insoluble dyestufis on the fiber according to the ice-colormethod or one, of the usual printing methods, for instance, in direct printing, or according to the known nitrosamine printing process or the like.

Theiyellow dyestuffs thus obtained are distinguished by their good all round fa'stness properties, particularly by very good fastness to soaping; a great number of them has also a high fastness to light.

- The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight, unless otherwise stated:

(1) 17.6 parts of 1-amino-2-methyl-4,5-dichlorobenzene are diazotized in the usual manner and the diazo-solution is coupled with a solution of 26.2 parts of l-(acetoacetylamino)--methoxy- 2-methyl-4-chlorobenzene in dilutecaustic soda solution to which there has been added Turkey red oil and the quantity of sodium acetate which is necessary to bind the mineral acid in excess. The separated dyestuff is filtered off and washed well. When produc'edin the usual manner, advantageously in the form of a paste on a substratum, it yields a greenish-yellow lake of high fastness to light. formula:

HaCO

01 (2) Bleached cotton yarn is grounded in a solution containing per liter: 1 (acetoacetyl-amino) 2-methoxy-t3-methyl-fl-chlorobenzenem grams 3 Caustic soda solution of 34 B cc 6 Turkey red oil co 5 Sodium chloride grams 100 Grams Sodium carbonate 1 Soap 3 Sodium hydrosulfite 0.5

- A greenish-yellow dyeing of very good fastness to light is obtained. l

The dyestufl has the following The dyestuff may also be produced on other vegetable fibers, on native cellulose, for instance, linen or on regenerated cellulose, for instance,

A lemon-yellow dyeing of very good fastness to light is thus obtained.

(4) Desized and bleached cotton piece goods viscose artificial silk, and also on wool and other are printed with the following paste: animal fibers, for instance, spun silk, on which a more reddish dyeing is obtained. fii gf s z sg igf dlchlolobenzene 1 (3) Desized and bleached cotton piece goods are padded on a foulard in a solution contain- 24 grgms 2 'i gg g 2 methoxy ing per liter: y cm 30 grams of Ca/US$ sodasolution of 34 Be. and 10 l-(acetoacetyl-amino)-2-methoxy-5 -meth- 20 grams of Turkey red oil are stirred into a yl-4-bromobenzene "grams" paste with Caustic soda solution of 34 B- cc. 22.5 50 grams of water, then dissolved in Turkey red oil cc 356 grams of warm water and made up with 15 The grounded and dried material is passed 500 grzrrgslgoftneutral starch tragacanth thickthrough a diazosolution which is obtained in the following manner: .1 kilo of prmting color.

After drying the printed material is steamed ggz 2: gg:a for 3 minutes in a moist state or exposed to the 20 0 air over-night and thereupon passed at 80 C. to 3% f i g i f z f g g g C 90'" 0. through a "solution containing per liter 20 0 6 e S 1 n 18 0 cc. of acetic acid of 50% strength, rinsed and and diazotized with an aqueous solution vsoaped of 3.6 grams of sodium nitrite. Thereupon, there i g 3 punt of very good fastness to are added 1g 18 o aine 7 rams of or stallized sodium acetate and The process may be earned out m the same 20 i f c ti y id of 507 stren th and the manner also with other diam-compounds and 9 Egg u t a g other aceto-acetic acid arylides of this series. 1 e is e p 0 The following table indicates a number of tints 1 of some other azo dyestuffs obtainable accord- The material is then exposed to .the air for ing to the present invention:

Aceto-acetyl compound of Coupled with the diam-compound oi- Tint 1-amino-2'methoxy-5-methyl-4-chlorobenzene l-amino-2-methyl-fi-chlorobeuzene. Lemon-yellow.

do l-amino-2-methyl-4-chlorobenzene. Yellow.

l-amino-2-methyl-3-chlorobenzene Lemon-yellow. Lamina-2,5-dichlorobenzene.- Greeuish-yellow.

I Lamina-2, 3, 4-trichlorobenzeno.. 1-amino-2 phenoxy-5-chlorobenze l-aminom 1-amino-4-methyl-2, 5-dichlorobenzene 1-amino-2-methoxy-5-chlorobenzene l-amino-2-methoxy-B-chlorobenzene.

-2-methoxy-5-methyl 1-amino-2-methyl-5-chlorobenzene.

1-amino-2-ethoxy-5-chlorobenzene 1-amino-2ethoxy-4-bromo-5-ohlorobenzene 1-amino-2-methoxy-4, fi-dichlorobenzene Do. Lemon-yellow.

Do. Yellow. Lemon-yellow.

Greenish yellow.

Lemon-yellow.

Greenish yellow.

Yellow.

Lemon-yellow.

Yellow: Lemon-yellow.

l-amino-2-methyl-3-chlorobenzcne Do. 1-amino-2, S-dichlorobenzene. Yellow. 1-amino-2, 3. 4-trichlorobenzene Greenish yellow. 1-amino-3-methyl-2, 4-dichlorobenzene Do. l-amino-2-methoxy5-chlorobenzene. Lemon-yellow. l-amino-Zi-methyl-i, G-dichlorobenzene Do. 1-amino-2-phenoxy-5-chlorobenzene Do. 1-an1ino-2A4-chlorphenoxy)-5-chlorobeuzene Greenish yellow. 1-21mino-2-(naphthyl-Z-hydroxy) -5-chlorobenzene Yellow. i'amino-2-methy1-5-bromobenzene Lemon-yellow. 1-amino-2-methyl-3, 4-dichlorobenzene o. 1-amino-2-methyl-4, 5-dichlorobenzene Greenish yellow. i-amino4-methyl-2, 3-dichlorobenzenc.. Do. l-amino-2-methoxy-Zi-chlorobenzene- Lemon-yellow. l-amino-2ethoxy-5-chlorobenzene Greenish yellow. l-amino-Z-ethoxyA-bromo-5-chlorobenzenc Do. l'aminoQ-methoXyl, 5-dichlorobenzene.. Lemon-yellow. l-amino-2-methyl-3clilorobenzene Greenish yellow. 1-amino-2-methy1-4-bromobenzene. Lemon-yellow. 1-amino-2-methyl-fi-bromobenzene. Do. l-amino-2-methyl-4-iodobenzene .u- Yellow. l-amino-2-methyl-4, Michhrobenzeno. Lemon-yellow. l-amino-4-methyl-2, 5-dichlorobenzcne. Do. l'amino-4-methyl-2. 3-dich1orobenzene- Do. l-amino-Z-methyl-4-bromo-5-cl1lorobenzene. Do. l-amino-2-ethoxy-4-bromo-5-chlorobenzene. Do. l-aminoa. 5-dimethoxyi-bromobeuzene. Yellow. l-amino-2-phenoxy-3-chlorobenzeneo. l-amino-2-methyl-5-chlorobenzene. Do. l-emino-2-methyl-3-chlorobenzeue- Greenish yellow. l-amino-3-methyl-2, i-dichlorobenzene..- Yellow. 1-amino-2-phenoxy-5-chlorobenzene Do.

. l-amino-2-methyl-4-bromobenzenc Lemon-yellow.

l-amino-2-methyl-4, S-dichlorobenzene Yellow. 1amino-2-methyl-4-bromo-5-chlotobenzene. Reddish yellow. l-amino-2ethoxy-4-bromo-5-chlorobenzene. D0. l-amino-3-methyl-4, G-dichlorobenzene Yellow.

7 a short time, repeatedly rinsed with cold water and finally soaped at boiling temperature.

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water and alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim:

1. The Water-insoluble azo dyestufi of the following formula:

yielding, when produced on the fiber, greenishyellow dyeings of good fastness properties, particularly of very good fastness to soaping and to light.

2. The water-insoluble azo dyestuff of the following formula:

OOH:

yielding, when produced on the fiber, lemon-yellow dyeings of good fastness properties, particularly of very good fastness to soaping and to light.

3. Fiber dyed with the water-insoluble azo dyestuif as claimed in claim 1.

4. Fiber dyed with the water-insoluble azo dyestufi as claimed in claim 2.

5. The water-insoluble azo dyestufis of the following general formula:

C Ha

ARTHUR ZITSCHER. ROBERT SCHMITT. HERBERT KRACKER.

CERTIFICATE OF CORBE C'II ON fatent No. 2 ,lh2,59b,. January 5, I959.

ARTHUR ZITSCHER, ET AL.

It is hereby certi fied that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, in the tab 1e, item'Y, in the column under the heading- "Coupled with the diazocompound of-", for 2.-methyl-phenoxy) read (2'-methy1phenoxy); item 8,

for ".(h-methoxy-phenfiy) read -methoxy-phenoxy) item 27, for (h-ch'lorphenoxy) read (LU-chlorphenoxy); item 28, for (naphthyl-Z-hydrOxy) read (naphthyl-2'-hydroxy); item L B, in the column under the heading "Acetoacetyl compound of-", for "IL-amino-Z-ethoxy-5-ethyl-h-ohlorobenzene read v 1- amino- 2- ethoxy- 5-methylchlorobenzeneand that the said Letters Patent -should be read with this correction therein that the same may conform to the record of the case in the Patent Office. v

Signed and sealed this 25th day of April, A.D. 1.9.59.

Henry Van Arsdale (569.1) v Acting Commissioner of Patents. 

